CN103589983A - Method for enhancing bonding strength of titanium carbide coating and titanium alloy substrate - Google Patents

Method for enhancing bonding strength of titanium carbide coating and titanium alloy substrate Download PDF

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Publication number
CN103589983A
CN103589983A CN201310594290.2A CN201310594290A CN103589983A CN 103589983 A CN103589983 A CN 103589983A CN 201310594290 A CN201310594290 A CN 201310594290A CN 103589983 A CN103589983 A CN 103589983A
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China
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alloy
nickel
carbide coating
bonding strength
plating
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CN201310594290.2A
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王志平
孙振
江云飞
孙波
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Civil Aviation University of China
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Civil Aviation University of China
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Abstract

The invention discloses a method for enhancing bonding strength of a titanium carbide coating and a titanium alloy substrate. The method comprises the following steps: firstly, electroplating nickel on the surface of Ti-6Al-4V alloy; secondly, through heat treatment, penetrating a nickel layer into the surface of the Ti-6Al-4V alloy better to form a nickel-titanium transition layer; finally, spraying the surface of the alloy by adopting a high-velocity oxy-fuel spraying technology to form the tungsten carbide coating. Through the adoption of the method, not only the bonding strength can be improved, but also the oxidization isolating effect is achieved to reduce oxidization of the Ti-6Al-4V alloy, therefore, the bonding strength of the titanium carbide coating and the Ti-6Al-4V alloy is improved.

Description

A kind of for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength
Technical field
The invention belongs to surface protection technique field, particularly relate to a kind of for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength,
Background technology
Ti-6Al-4V alloy is typical (alpha+beta) type diphasic titanium alloy, due to it, there is the series of advantages such as good solidity to corrosion, low density and good toughness and weldability, therefore be widely used in civil and military aerospace industry, for example various beams, bulkhead, the slide rail of flyer and rise and fall and set a roof beam in place, the fan of aircraft engine, gas compressor blade dish and blade, the housing of space rocket and pressurized vessel, and various types of fastening pieces etc.But, because Ti-6Al-4V alloy has the poor shortcoming of surface abrasion resistance, so be greatly affected work-ing life.For this reason, must take adequate measures to protect its surface, to improve use properties and the life-span of structural part.Utilize wolfram varbide (WC) coating prepared by hypersonic flame spraying technology to there is very high wear resisting property, by the desirable means that are titanium alloy surface protection.Hypersonic flame spraying technology is a kind of HVOF (High Velocity Oxygen Fuel) technology growing up the eighties in last century, its outstanding feature is flying speed of partcles high (can reach 700m/s), Heating temperature low (being about 3000 ℃), is particularly suitable for labile tungsten-carbide cermet coating after spraying-and-heating.The bonding strength high (>=80Mpa) of this coating, density large (hole ﹤ 1%), hardness high (>=HV1000), therefore have good wear resisting property.
Yet study discovery through scientific research personnel; although this, utilize WC coating prepared by hypersonic flame spraying technology can greatly improve the wear resisting property of titanium alloy surface; but it is not high with the bonding strength of titanium alloy; and along with the increase in working strength and life-span; easily produce layering and lost efficacy, thereby order protection effect is had a greatly reduced quality.By further research, find, the high temperature that spraying process Flame produces has caused titanium alloy surface oxidation, zone of oxidation and anchoring strength of coating are low is the most important reason that causes inefficacy, and therefore reducing the degree of oxidation of titanium alloy in spraying process is the point of penetration that improves bonding properties.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength.
In order to achieve the above object, provided by the inventionly for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength, comprise the following step carrying out in order:
1) grinding process is carried out to fine sandpaper in the surface of Ti-6Al-4V alloy, to remove surface oxide layer;
2) in pH value, be 5.6～5.9, temperature is that 43～60 ℃ and cathode current density Dk are 2.0～10Adm -2condition under the Ti-6Al-4V alloy after above-mentioned polishing is carried out to plating nickel on surface processing with plating solution, until form the nickel dam of 0.2 ± 0.01mm;
3) the Ti-6Al-4V alloy after above-mentioned nickel plating is heat-treated to 4h under argon shield at the temperature of 720 ℃, to promote the diffusion of nickel and the formation of Ni-Ti transition layer;
4) nickel dam of the Ti-6Al-4V alloy surface after above-mentioned thermal treatment is carried out to pre-grinding processing with fine sandpaper, to remove surface oxide layer;
5) utilize the Ti-6Al-4V alloy surface of hypersonic flame spraying technology after above-mentioned pre-grinding to spray, coated powder material is WC-17Co, until form thickness, is the tungsten carbide coating of 200-300 μ m.
Described step 2) in every liter of plating solution in, contain 179-181g NiSO 4.6H 2o, 24-26gNH 4cl and 29-31g H 3bO 3.
The processing condition of described step 5) moderate supersonic speed flame plating are: take aviation kerosene as fuel, take oxygen as ignition dope, take argon gas as powder feeding gas, in spraying process, aviation kerosene oil flow is 23L/h, oxygen flow is 55000slph, powder feeding gas flow is 12L/min, and spray distance is 380mm, and spraying rate is 300mm/s.
Provided by the invention is first electroplating nickel on surface processing to be carried out in the surface of Ti-6Al-4V alloy for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength, by heat treated mode, make nickel dam can penetrate into better alloy surface again, form Ni-Ti transition layer, not only can improve bonding strength like this, but also play the isolated effect being oxidized, reduce Ti-6Al-4V alloy and occur oxidation, thereby improved the bonding strength between coating and Ti-6Al-4V alloy.
Accompanying drawing explanation
Fig. 1 is the SEM image after the nickel plating of Ti-6Al-4V alloy surface.
Fig. 2 (a) is Ti-6Al-4V alloy surface EDS collection of illustrative plates before nickel plating; Fig. 2 (b) is the EDS collection of illustrative plates of Ni-Ti transition layer after nickel plating and thermal treatment.
Fig. 3 (a) is for not carrying out Nickel Plating Treatment, only the EDS image after four-point bending through the Ti-6Al-4V alloy of hypersonic flame spraying; Fig. 3 (b) is for through Nickel Plating Treatment, and through the Ti-6Al-4V alloy of hypersonic flame spraying the EDS image after four-point bending.
Fig. 4 (a) and Fig. 4 (b) are respectively and do not carry out Nickel Plating Treatment, only through the Ti-6Al-4V alloy of hypersonic flame spraying and through Nickel Plating Treatment, and the Ti-6Al-4V alloy fracture energy release rate calculation result schematic diagram of process hypersonic flame spraying.
Embodiment
Below in conjunction with the drawings and specific embodiments, to provided by the invention, for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength, be elaborated.
Embodiment 1:
What the present embodiment provided comprises for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength the following step carrying out in order:
1) grinding process is carried out to 1200 order fine sandpapers in the surface of Ti-6Al-4V alloy, to remove surface oxide layer;
2) in pH value, be 5.6, temperature is that 45 ℃ and cathode current density Dk are 2.0Adm -2condition under the Ti-6Al-4V alloy after above-mentioned polishing is carried out to plating nickel on surface processing with plating solution, in every liter of plating solution, contain 179g NiSO 4.6H 2o, 24g NH 4cl and 29g H 3bO 3, until form the nickel dam of 0.2 ± 0.01mm;
3) the Ti-6Al-4V alloy after above-mentioned nickel plating is heat-treated to 4h under argon shield at the temperature of 720 ℃, to promote the diffusion of nickel and the formation of Ni-Ti transition layer;
4) nickel dam of the Ti-6Al-4V alloy surface after above-mentioned thermal treatment is carried out to pre-grinding processing with 1200 order fine sandpapers, to remove surface oxide layer;
5) utilize the Ti-6Al-4V alloy surface of hypersonic flame spraying technology after above-mentioned pre-grinding to spray, coated powder material is WC-17Co, the processing condition of hypersonic flame spraying are: take aviation kerosene as fuel, take oxygen as ignition dope, take argon gas as powder feeding gas, in spraying process, aviation kerosene oil flow is 23L/h, oxygen flow is 55000slph, powder feeding gas flow is 12L/min, spray distance is 380mm, spraying rate is 300mm/s, until form thickness, is the tungsten carbide coating of 200-300 μ m.
Embodiment 2:
What the present embodiment provided comprises for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength the following step carrying out in order:
1) grinding process is carried out to 1200 order fine sandpapers in the surface of Ti-6Al-4V alloy, to remove surface oxide layer;
2) in pH value, be 5.7, temperature is that 50 ℃ and cathode current density Dk are 6.0Adm -2condition under the Ti-6Al-4V alloy after above-mentioned polishing is carried out to plating nickel on surface processing with plating solution, in every liter of plating solution, contain 180g NiSO 4.6H 2o, 25g NH 4cl and 30g H 3bO 3, until form the nickel dam of 0.2 ± 0.01mm;
3) the Ti-6Al-4V alloy after above-mentioned nickel plating is heat-treated to 4h under argon shield at the temperature of 720 ℃, to promote the diffusion of nickel and the formation of Ni-Ti transition layer;
4) nickel dam of the Ti-6Al-4V alloy surface after above-mentioned thermal treatment is carried out to pre-grinding processing with 1200 order fine sandpapers, to remove surface oxide layer;
5) utilize the Ti-6Al-4V alloy surface of hypersonic flame spraying technology after above-mentioned pre-grinding to spray, coated powder material is WC-17Co, the processing condition of hypersonic flame spraying are: take aviation kerosene as fuel, take oxygen as ignition dope, take argon gas as powder feeding gas, in spraying process, aviation kerosene oil flow is 23L/h, oxygen flow is 55000slph, powder feeding gas flow is 12L/min, spray distance is 380mm, spraying rate is 300mm/s, until form thickness, is the tungsten carbide coating of 200-300 μ m.
Embodiment 3:
What the present embodiment provided comprises for strengthening the method for tungsten carbide coating and titanium alloy substrate bonding strength the following step carrying out in order:
1) grinding process is carried out to 1200 order fine sandpapers in the surface of Ti-6Al-4V alloy, to remove surface oxide layer;
2) in pH value, be 5.9, temperature is that 60 ℃ and cathode current density Dk are 10Adm -2condition under the Ti-6Al-4V alloy after above-mentioned polishing is carried out to plating nickel on surface processing with plating solution, in every liter of plating solution, contain 181g NiSO 4.6H 2o, 26g NH 4cl and 31g H 3bO 3, until form the nickel dam of 0.2 ± 0.01mm;
3) the Ti-6Al-4V alloy after above-mentioned nickel plating is heat-treated to 4h under argon shield at the temperature of 720 ℃, to promote the diffusion of nickel and the formation of Ni-Ti transition layer;
4) nickel dam of the Ti-6Al-4V alloy surface after above-mentioned thermal treatment is carried out to pre-grinding processing with 1200 order fine sandpapers, to remove surface oxide layer;
5) utilize the Ti-6Al-4V alloy surface of hypersonic flame spraying technology after above-mentioned pre-grinding to spray, coated powder material is WC-17Co, the processing condition of hypersonic flame spraying are: take aviation kerosene as fuel, take oxygen as ignition dope, take argon gas as powder feeding gas, in spraying process, aviation kerosene oil flow is 23L/h, oxygen flow is 55000slph, powder feeding gas flow is 12L/min, spray distance is 380mm, spraying rate is 300mm/s, until form thickness, is the tungsten carbide coating of 200-300 μ m.
In order to verify effect of the present invention, the inventor utilizes the Ti-6Al-4V alloy structure after nickel plating and thermal treatment that scanning electron microscope is prepared above-described embodiment to observe, by Fig. 1, can clearly be found out, the Ti-6Al-4V alloy after nickel plating and thermal treatment is divided into three layers: plated surface nickel dam, middle Ni-Ti transition layer and titanium alloy substrate.
Fig. 2 (a) is Ti-6Al-4V alloy surface EDS collection of illustrative plates before nickel plating; Fig. 2 (b) is the EDS collection of illustrative plates of Ni-Ti transition layer after nickel plating and thermal treatment.Analyze and find, after nickel plating and thermal treatment, between nickel dam and Ti-6Al-4V alloy, forming a layer thickness is the Ni-Ti transition layer of 0.05mm, Ni-Ti transition layer after Ti-6Al-4V alloy surface and nickel plating and thermal treatment before nickel plating is carried out to ultimate analysis known, in Ni-Ti transition layer, oxygen level obviously reduces, illustrate that this transition layer has stoped the diffusion of oxygen, greatly reduced the oxidation that in spraying process, Yin Gaowen causes, promoted the combination of coating and matrix.Before nickel plating, after Ti-6Al-4V alloy surface and nickel plating and thermal treatment, the compositional analysis result of Ni-Ti transition layer is shown in respectively table 1 below, table 2.
Table 1
Element Wt% At%
CK 07.78 21.08
OK 11.26 20.93
AlK 05.91 07.13
TiK 72.31 49.11
VK 02.75 01.75
Table 2
Element Wt% At%
CK 03.74 13.58
OK 03.06 08.35
AlK 02.43 03.93
TiK 39.61 36.10
VK 51.16 38.04
In addition, the inventor also utilizes Inston universal tensile testing machine to not carrying out Nickel Plating Treatment, only through the Ti-6Al-4V alloy of hypersonic flame spraying and through Nickel Plating Treatment, and the Ti-6Al-4V alloy through hypersonic flame spraying has carried out four-point bending experiment, specimen size is 120mm * 15mm * 3mm, and loading velocity is 0.1mm/min.Then utilize scanning electron microscope to observe above-mentioned two kinds of alloy structures.Fig. 3 (a) is for not carrying out Nickel Plating Treatment, only the EDS image after four-point bending through the Ti-6Al-4V alloy of hypersonic flame spraying; Fig. 3 (b) is for through Nickel Plating Treatment, and through the Ti-6Al-4V alloy of hypersonic flame spraying the EDS image after four-point bending.As can be seen from the figure, the bonding properties of the former tungsten carbide coating and Ti-6Al-4V alloy is poor, and both are easy to occur interfacial failure, and crack propagation is longer; And after nickel plating due to the existence of Ni-Ti transition layer, the bonding properties of tungsten carbide coating and Ti-6Al-4V alloy is very significantly improved, both are not easy to tear, crack propagation is shorter.
In addition, the inventor is also to the above-mentioned Nickel Plating Treatment of not carrying out, only through the Ti-6Al-4V alloy of hypersonic flame spraying and through Nickel Plating Treatment, and through the Ti-6Al-4V alloy of hypersonic flame spraying, carried out the calculating of fracture energy release rate, every group 5, result is shown in respectively Fig. 4 (a) and Fig. 4 (b).Mean breaking energy release rate: Ga=271.38J.m in Fig. 4 (a) 2, mean breaking energy release rate: Gb=475.06J.m in Fig. 4 (b) 2, as can be seen here, the latter, apparently higher than the former, illustrates that interfacial combined function increases.

Claims (3)

1. for strengthening a method for tungsten carbide coating and titanium alloy substrate bonding strength, it is characterized in that: described method comprises the following step carrying out in order:
1) grinding process is carried out to fine sandpaper in the surface of Ti-6Al-4V alloy, to remove surface oxide layer;
2) in pH value, be 5.6～5.9, temperature is that 43～60 ℃ and cathode current density Dk are 2.0～10Adm -2condition under the Ti-6Al-4V alloy after above-mentioned polishing is carried out to plating nickel on surface processing with plating solution, until form the nickel dam of 0.2 ± 0.01mm;
3) the Ti-6Al-4V alloy after above-mentioned nickel plating is heat-treated to 4h under argon shield at the temperature of 720 ℃, to promote the diffusion of nickel and the formation of Ni-Ti transition layer;
4) nickel dam of the Ti-6Al-4V alloy surface after above-mentioned thermal treatment is carried out to pre-grinding processing with fine sandpaper, to remove surface oxide layer;
5) utilize the Ti-6Al-4V alloy surface of hypersonic flame spraying technology after above-mentioned pre-grinding to spray, coated powder material is WC-17Co, until form thickness, is the tungsten carbide coating of 200-300 μ m.
2. method according to claim 1, is characterized in that: in every liter of plating solution described step 2), contain 179-181g NiSO 4.6H 2o, 24-26g NH 4cl and 29-31g H 3bO 3.
3. method according to claim 1, it is characterized in that: the processing condition of described step 5) moderate supersonic speed flame plating are: take aviation kerosene as fuel, take oxygen as ignition dope, take argon gas as powder feeding gas, in spraying process, aviation kerosene oil flow is 23L/h, and oxygen flow is 55000slph, and powder feeding gas flow is 12L/min, spray distance is 380mm, and spraying rate is 300mm/s.
CN201310594290.2A 2013-11-22 2013-11-22 Method for enhancing bonding strength of titanium carbide coating and titanium alloy substrate Pending CN103589983A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106694659A (en) * 2015-07-31 2017-05-24 宝山钢铁股份有限公司 Deburring roller and manufacture method thereof
TWI667764B (en) * 2018-06-29 2019-08-01 大陸商長江存儲科技有限責任公司 Semiconductor structure and method of forming the same
US11571692B2 (en) * 2017-06-23 2023-02-07 PhysioLogic Devices, Inc. Attachment method for microfluidic device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558360A (en) * 1978-10-19 1980-05-01 Satoosen:Kk Forming method for heat and abrasion resisting protective coating
US5116430A (en) * 1990-02-09 1992-05-26 Nihon Parkerizing Co., Ltd. Process for surface treatment titanium-containing metallic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5558360A (en) * 1978-10-19 1980-05-01 Satoosen:Kk Forming method for heat and abrasion resisting protective coating
US5116430A (en) * 1990-02-09 1992-05-26 Nihon Parkerizing Co., Ltd. Process for surface treatment titanium-containing metallic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姬寿长，等: "Ti6Al4V合金表面超音速火焰喷涂WC-12Co涂层组织及相分析", 《稀有金属材料与工程》, vol. 41, no. 11, 30 November 2012 (2012-11-30) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106694659A (en) * 2015-07-31 2017-05-24 宝山钢铁股份有限公司 Deburring roller and manufacture method thereof
US11571692B2 (en) * 2017-06-23 2023-02-07 PhysioLogic Devices, Inc. Attachment method for microfluidic device
TWI667764B (en) * 2018-06-29 2019-08-01 大陸商長江存儲科技有限責任公司 Semiconductor structure and method of forming the same

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Application publication date: 20140219